DE2318762B2 - PROCESS FOR STAINING FIBERS FROM PHENOLIC RESINS - Google Patents

Description

R '

R — C — N

Il ο

R "

IO

in which R, R ' and R ", which can be the same or different from one another, denote hydrogen, an alkyl group having 1 to 3 carbon atoms, a phenyl, benzyl or phenethyl group, but R ₁ R' and R" are not simultaneously hydrogen atoms can be, and that the dyed fibers are then washed thoroughly to remove the amide compound.

2. The method according to claim 1, characterized in that that a dye bath is used which also contains (1) at least one metal sulfate or (2) at least one oxygen-containing compound from the group of the alkenols with 3 to 5 Carbon atoms, benzyl alcohol, tetrahydrofurfuryl alcohol, dioxane, the dialkyl ketones with 3 to 5 Carbon atoms, cyclohexanone and the lower alkyl esters of formic acid and acetic acid or that contains (1) and (2).

3. The method according to claim 1 or 2, characterized in that the metal sulfate or the Oxygen-containing compound or both in an amount of 3 to 35% by weight based on the Total weight of the dyebath, used.

4. The method according to any one of claims 1 to 3, characterized in that the amide compound used in an amount of 3 to 10% by weight, based on the total weight of the dyebath.

5. The method according to any one of claims 1 to 4, characterized in that there is a dye bath used that in the form of a dye-containing solution or in the form of a Dye-containing printing paste is present.

6. The method according to claim 5, characterized in that the dye is a disperse dye, an azo dye, a cationic dye or a vat dye is used.

7. The method according to any one of claims 1 to 6, characterized in that the dyeing carried out by immersion at a bath temperature of 80 to 140 ° C.

8. The method according to any one of claims 1 to 6, characterized in that the dyeing is carried out in (> o the way that a paste-like dye bath is padded on the phenolic resin fibers and then 10 to 60 minutes at 110 to 140 ⁰ C with Treated with steam.

9. A method according to any one of claims 1 to 6, f> .s characterized in that one carries out the printing in such a way that applying a paste-like dye bath to the phenolic resin fibers, and then 10 to 60 minutes at 110 to 14O ⁰ C treated with water stew.

The invention relates to a method for dyeing fibers made from phenolic resins. In particular it concerns a process for uniformly dyeing fibers made of phenolic resins in deep shades with good Authenticity properties.

As is known, fibers made of phenolic resin (hereinafter simply referred to as phenolic resin fiber) have one low affinity for dyes and extremely poor dyeability, for example green ones their compact fiber structure, the lack of dye-affine groups or their high negative Surface potential. It is therefore very difficult to evenly use phenolic resin fibers in deep real shades to color.

Other fibers with a compact fiber structure and without dye-affine groups, such as. B. polyester fibers or polypropylene fibers, are used at a temperature of up to 110 to 130 ° C of dyes with a small molecular volume or using a carrier such as coloring liquid containing o-phenylphenol, chlorobenzene, salicylic acid ester or benzoic acid ester, satisfactory colorations are obtained.

In contrast, phenolic resin fibers can selbsl at temperatures of 110 to 130 ⁰ C using a carrier, as described above, are practically hardly stained, and it has been difficult to produce colored phenolic resin fibers that are useful for practical applications.

Certain types of such difficult-to-dye synthetic fibers have heretofore been, for example, after a r Dyed method in which a substance having an affinity for dye, e.g. B. a polymer mil a free amino group is incorporated into a spinning solution and when this solution is spun obtained fibers are dyed by conventional methods. In addition, there was a process for this applied, in which a pigment was incorporated into a spinning solution and the spinning solution under Formation of Dyed Fibers Was Spun In accordance with another method, a pigment was made fixed on the surface of the fibers with the help of a: binder to zi the colored fibers obtain.

However, if such methods of dyeing were used prior to phenolic fiber, they were results obtained are unsatisfactory. If z. B. a connection with a functional group, ζ. Β Hydrazine, which can be bound to a dye, or an organic or inorganic pigment a molten prepolymer of the phenolic resin type added and the mixture spun unc is cured, the strength of the phenolic resin fibers decreases markedly after curing, or the desired one Non-flammability of the phenolic resin fibers is dadurcl impaired. On the other hand, when the phenolic fiber is obtained by fixing a pigment on its surface colored using a binder, those obtained were found to be more colored Fibers because of their poor fastness properties or their hard surface as unusable

Also, many binders that can be applied for this purpose make up the phenolic resin fibers flammable and therefore affect their most desirable property, namely their non-flammability.

Thus, the usual methods of dyeing synthetic fibers can not be satisfactory for Dyeing of phenolic resin fibers can be applied, and therefore there has long been an interest in the Development of a dyeing process for dyeing phenolic fibers that gives good results and can be used technically.

The object of the invention is therefore to create an improved method for dyeing fibers from Phenolic resins, whereby even colorations can be achieved in deep, true shades and where this process can be carried out on an industrial scale in an advantageous manner.

This object is achieved according to this invention by a method for coloring Fibers made from phenolic resins, which is characterized in that the fibers are treated with an aqueous dye bath treated as a dyeing aid 3 to 50 wt .-%, based on the total weight of the dye bath, contains at least one amide compound of the general formula (1):

R

/
R — C — N

Il \

O R "

in which R, R 'and R ", which can be the same or different from one another, represent hydrogen and an alkyl group with 1 to 3 carbon atoms, a phenyl, benzyl or phenylethyl group, but where R, R ' and R "cannot be hydrogen atoms at the same time, and that the colored fibers are subsequently Wash thoroughly to remove the amide compound.

The term "staining or staining" as used herein is used in its broadest sense and includes (a) dipping dyeing in which a fiber material is dipped in a Dye solution is stained, (b) dyeing by padding, in which a dye solution is on a Fiber material is padded and this is then heated, and (c) printing, in which a printing paste is applied Fiber material is applied and this is then heated to color the printed parts.

Accordingly, the dye bath used in the method according to the invention can be in the form of a a dye-containing solution (especially in the case of dip dyeing) or in the form of a Paste containing dye (especially when staining by padding and printing).

A typical composition for such a dyebath is given below, although the Invention is not limited to this.

Composition of the dye bath for dyeing by dipping and padding

Dye in an about 0.01 to about 30 wt .-% of the material to be colored

Amide compound of the formula I given above in the amount given below:
Viscosity- absent or present in a small amount of the regulator

water

rest

Composition of the dye bath for printing
Dye in an amount corresponding to about 5 to about 50% of the total weight of the dyebath
Thickening in about 0.1 to about 10% of the average *) total weight of the dyebath ent

talking crowd

_IS amide compound of the above formula I in the following amount:

water

rest

*) Examples of thickeners are nairium alginate, Tragacanth gum, starch, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, carboxymethyl starch, Gelatin, dextrin, starch gum, polyvinyl alcohol, kerosene and 1,1,3-trichloroethane.

The term "phenolic resin fibers (phenolic resin fibers)" used here means uncured Fibers by melt spinning or by wet spinning and the like. A prepolymer from Novolak or resol type made from a phenol (e.g. phenol, cresol, xylenol, ethylphenol, phenylphenol, amylphenol, bisphenol A or resorcinol) and one Aldehyde (e.g. formaldehyde, acetaldehyde, paraformaldehyde, hexamethylenetetramine, furfural, glutaraldehyde or glyoxal), or to understand the hardened products thereof made by Curing these uncured fibers with a curing agent such as an aldehyde in the presence of an alkaline one or acidic catalyst.

Those to be colored by the method according to the invention Phenolic resin fibers can consist of a phenolic resin alone or a mixture of a predominant Proportion of one phenolic resin and a minor proportion (generally 1 to 40% by weight) of another fiber-forming polymer exist. However, in order not to impair the non-flammability of the phenolic resin, the amount of the other fiber-forming polymer should be as small as possible, preferably up to 30% by weight.

Specific examples of fiber-forming polymers that can be used according to the invention, are polyamide resins such as nylon 6, nylon 11, nylon 12, Nylon 66, nylon 610, nylon 611, nylon 612, and blends of two or more of these resins with each other; Polyester resins such as polyethylene terephthalate, Polyesters derived from the same structural elements, such as polyethylene terephthalate, in which a part of ethylene glycol is replaced by other known glycols, derived from the same structural elements Polyesters, such as polyethylene terephthalate, in which the terephthalic acid is replaced by o- or m-phthalic acid, others

do known aliphatic dicarboxylic acids or mixtures is composed of two or more of these with one another. Polyester ethers such as polyethylene hydroxybenzoate and Polyolefin resins such as polyethylene, polypropylene and ethylene / propylene copolymers or mixtures

(> s from two or more of these products together.

The term used "fibers made from phenolic resins" also denotes a fiber product, for example a ribbon, a yarn, a fabric, a knitted fabric, a

Knitwear, a carpet, a non-woven fabric or a laminated fabric made of phenolic resin fibers alone or a composite of phenolic resin fibers and other natural fibers, semi-synthetic fibers or synthetic fibers Fibers. S.

Most of the dyes commonly used for coloring natural, semi-synthetic or synthetic Fiber materials can also be used in the method according to the invention for dyeing Phenolic resin fiber materials can be used. For example, vat dyes, azo dyes, cationic dyes, disperse dyes, metal-containing dyes, acidic dyes, direct dyes, Reactive dyes and chromium dyes can be used. Among these dyes, the azo dyes the cationic dyes, the disperse dyes and the vat dyes have good dyeing properties in with respect to phenolic fibers and they can be used to advantage in the present invention. Typical Examples of these dyes are as follows:

(1) Cationic dyes:

Cationic dyes from azo, diphenylmethane, triphenylmethane, xanthene, acridine, quinoline, methine, Thiazole, azine, thiazine and oxyzine types. Specific examples of this are CI. Basic Orange 21 (C.J. 68035), CI. Basic Red 15, CI. Basic Violet 7 (C J. 48020), C. I. Basic Orange 30, C. I. Basic Blue 22, CL Basic Red 35, CI. Basic Blue 59, CI. basic Green 77 and C. I. Basic Violet 26.

(2) disperse dyes

Azo, anthraquinone, nitro, aminoquinone and methine type disperse dyes. Specific examples for this are: Cl. Disperse Orange 51, CI. Disperse Red 146, CI. Disperse Red 129, C I. Disperse Violet 30, CI. Disperse Red 55, CI. Disperse Red 60, CI. Disperse Blue 71 and C.I. Disperse Blue 55.

(3) azo dyes

Examples of the nitrogen-containing diazo component are: C. I. Azoic Diazo Component 41 (C. 1.37165), C. I. Azoic Diazo Component 48 (C. 1.37235), C I. Azoic Diazo Component 118, CI. Azoic Diazo Component 124, CI. Azoic Diazo Component 125 and the like. Examples of the nitrogen-containing coupling component are C I. Azoic Coupling Component 8 (C 1.37525), C I. Azoic Coupling Component 11 (C 1.37535), C. I. Azoic Coupling Component 17 (C I 37515), C. I. Azoic Coupling Component 35 (C 1.37615) and the like. C I. Azoic Red 79, C.I. Azoic Red 81, CI. Azoic Blue 30, C I. Azoic Green 1 and C. I. Azoic Brown 15.

(4) vat dyes

Anthraquinone and indigozoyl type vat dyes. Specific examples are: C. I. Vat (> o Orangel4, C.I. Vat Red 41, (C I. 73300), Cl. Vat Violet 13 (C. I. 68700), C. I. Vat Blue 20 (C. I. 59800), C. I. Vat Green 26 and C. I. Vat Brown 56.

The alkyl group of the substituents R, R 'and R "in the general formula I can be an unbranched or (> s be a branched alkyl group. Examples of such alkyl groups are methyl, ethyl, n-propyl or i-propyl groupc. Examples of amide compounds used in the dye bath according to the invention are the following:

Acetamide, acetomethylamide, acetoethylamide, acetopropylamide, formmethylamide, formethylamide, formpropylamide, formanilide, acetanilide, NN-dimethylformamide, N.N'-diethylformanilide, NN-dipropylformamide, NN-diphenylformamide, NN-diphenylformamide, N, N-dimethylacetamide, N, N-dimethylacetamide , Ν, Ν-diphenylacetamide, benzamide, methylbenzamide, ethylbenzamide, propionbenzamide, NN-dimethylpropionylamide, N, N-diethylpropionylamide,
N, N-diphenylpropionylamide, N, N-dimethylbenzamide, N, N-diethylbenzamide, Ν, Ν'-dipropylbenzamide, N, N-diphenylbenzamide, propionamide, phenylanilide, propionylanilide, butylamide, and butylanilide.

These amide compounds can be used alone or in the form of mixtures of two or more components be used. Among these compounds are particularly preferred:

N, N'-dimethylformamide,
N.N'-dimethylacetamide, NN-diethylformamide, Ν, Ν-diethylacetamide, N, N-diphenylformamide, Ν, Ν-diphenylacetamide, methylbenzamide, benzamide, benzanilide, acetanilide, ethylbenzamide and propylbenzamide.

Particularly suitable amide compounds are N, N-diethylformamide, Ν, Ν-dimethylacetamide and N.N diethylacetamide.

The suitable concentration of the amide compound in the dye bath varies depending on the type the shape and the amount of the phenolic resin fiber material to be colored. The concentration is preferably 15.0 to 40.0% by weight. Within the invention applied concentration range, the amide compound leads to no impairment (deterioration) the physical properties of the phenolic resin fiber material and no trouble whatsoever when staining. When the concentration of the amide compound exceeds 50%, diffusion becomes the Compound in the inner structure of the fibers because of their extraordinarily great ability to take the dye dissolve, prevents, which in turn leads to a reduction in the dyeability (deterioration of the dying properties) leads. Even if the dye is temporarily fixed to the material, there is a risk of that it is dissolved, and the colorations obtained have only poor fastness properties on. In addition, the amide compound exerts a strong swelling effect on the phenolic resin fibers and reduces the strength of the fibers. On the other hand, if the concentration of the amide compound is less is than 3% by weight, the addition of the amide compound does not lead to an improved coloring effect.

The dyeing method for dyeing the phenolic resin fiber material by the method of the present invention does not differ from the usual methods, i.e. the fiber material can be used according to the usual Dyeing method using a dye bath containing a dye in the concentration given above contains, and if desired using a thickening agent, such as. B. gum tragacanth or Dextrin, and a common additive. According to a preferred embodiment of the In the process according to the invention, the dyeing temperature (temperature of the dye bath) is 80 to 140

preferably 100 to 130 ⁰ C, if dyed by immersion in an aqueous solution of a dye. If the temperature is below 8O ⁰ C, sufficient swelling effect is exerted on the phenolic resin fibers, and it is difficult to dye evenly in deep shades. On the other hand, if the temperature is above 140 ^° C., excessive swelling leads to a decrease in the strength of the phenolic resin fibers or to decomposition of the amide compound.

When the dyeing process is carried out by padding or printing, a solution or paste-like material containing a dye and the amide compound is padded (applied) to the material to be colored or printed, and then the material is treated with water vapor. The temperature of the steam is not critical, but it is advantageously from 110 to 140, preferably from 120 to 130 ^° C. The steam time is generally from 10 to 60 minutes.

The fiber material dyed in this way is then washed and dried. When a disperse dye is used, the dyed material by a conventional method with an aqueous solution which is maintained at a temperature of 60 to 8O ⁰ C and hydrogen sulfite (0.5 to 2 g / l), soda ash (0.3 is to 1 g / l) and a nonionic surfactant (0.5 to 2 g / l), washed for about 20 to 30 minutes. If the material is stained with other dyes, the stained material is suitably an aqueous solution, which is maintained at a temperature of 60 to 8O ⁰ C and contains a non-ionic oberflächenaktivies means (0.5 to 2 g / l), washed for about 20 to about 30 minutes. Since the amide compound generally has a tendency to remain on the dyed fibers as a result of adsorption on them, it is important that the material is sufficiently washed free of the amide compound, since the amide compound is somewhat flammable and toxic to the skin, resulting in a Would decrease the commercial value of the fiber product.

The effect of the amide compound on the phenolic resin fibers does not consist in a mere swelling effect of a common carrier used for dyeing synthetic fibers, such as phenol, dichlorobenzene, cresol or ethylene glycol, but also in a neutralizing effect of the negative charge on the surface of the fibers, which causes the dye to adsorb on the fibers and makes it light-sensitive. Therefore, this neutralization effect in connection with its swelling effect leads to an increased solubility of a dye or a paste, whereby the fiber material is colored in deep, real shades. This is evident from the fact that when a phenolic resin fiber material is treated with a dye tape containing a swelling agent such as phenol, dichlorobenzene or crosol, it is not dyed at all. In addition, phenolic resin fiber materials are known to be difficult to color evenly. According to the invention, however, this disadvantage is eliminated by the use of the amide compound and a uniform tinting is achieved.

In conventional dyeing of synthetic fibers using a carrier, a surfactant is usually added to improve the dispersibility of the carrier and to cause it to be uniformly absorbed onto the fibers. According to the present invention, the use of such a surface active agent can be omitted, and even in the absence of the surface active agent, it is possible to uniformly dissolve and disperse a dye or a dye paste by the amide compound and to allow the dye to penetrate to achieve coloration with a uniform deep hue support. In addition, the

ίο adsorption and diffusion of the dye because of the Neutralization of the negative charge on the surface of the phenolic resin fiber, promoted by the amide compound will. These advantages were due to the common state of the art for coloring phenol resin fibers not expected.

The improvement achieved in accordance with the invention in the dyeability of the phenolic resin fiber material by The action of the amide compound of the formula I is very remarkable, and so is the dyeing process which has been improved in this way is technically acceptable as such. The only difficulty encountered with the amide compound is that the stained material was thoroughly washed to completely remove the amide compound must become.

It has been found, however, that this difficulty can be overcome by working together with the amide compound (1) at least one water-soluble metal sulfate or (2) at least one oxygen containing compound from the group of alkenols with 3 to 5 carbon atoms, benzyl alcohol, tetrahydrofurfuryl alcohol, Dioxane, the dialkyl ketone with 3 to 5 carbon atoms, cyclohexanone and the lower Alkyl esters of formic acid and acetic acid or a mixture of (1) and (2) are incorporated into the dyebath.

When the amide compound and the oxygen-containing compound are present in the dye bath, a number of notable technical advantages can thereby be achieved. Be like that for example the diffusion of the dye into the

• to phenolic resin fiber material and its dyeability by the synergistic effect of the admid compound and the oxygen-containing compound improved even when the concentration of the amide compound is low. There is also an essential

.15 less tendency of the amide compound to be adsorbed on the surfaces of the phenolic resin fibers. Therefore, the amide compound can be completely removed by ordinary washing.
As component (1), any water-soluble

so metal sulfate can be used. Examples of suitable metal sulphates are sodium sulphate, potassium sulphate, beryllum sulphate, magnesium sulphate, aluminum sulphate, potassium alum, chromium sulphate, chrome alum, Elsen (III) sulphate, Elsen (III) sulphate, Elsen (II) ammonium sulphate, cobalt sulphate and Nlk

kelsulfat. Are sodium sulfate, potassium sulfate and cold alum particularly preferred. These metal sulfates can either alone or in a mixture of two! or several components are used.

The metal sulfate can be in a concentration of 3.0

(in up to 33.0 OeW ₁ - ¹ H) _1, preferably from 10.0 to 30.0% by weight, based on the total weight of the bath. If the concentration of the metal sulfate is more than 30.0%, it becomes difficult to dissolve it in the liquid. If his

(15 concentration is less than 3.0%, the Sulphate has no effect and, moreover, the amide compound becomes easier on the surface of the Phenolic resin fibers adsorbed, in this case the

709 631/467

Removal of the amide compound by washing is time consuming.

Examples of alkanols with 3 to 5 carbon atoms, which can be used together with the amide compound are n-propanol, iso-propanol, n-butanol, Isobutanol, sec-butanol, tert-butanol, N-amyl alcohol and sec-amyl alcohol. Examples of dialkyl ketones with 3 to 5 carbon atoms are acetone, methyl ethyl ketone and diethyl ketone. Examples of lower Alkyl esters of formic acid and acetic acid are methyl formate, ethyl formate, propyl formate, butyl formate, Methyl acetate, ethyl acetate, propyl acetate and butyl acetate. Particularly preferred are n-propanol, n-butanol, benzyl alcohol, dioxane and cyclohexanone.

The oxygen-containing compounds can be used alone or in admixture of two or more Components are used. The oxygen-containing compound is preferably with the Mixable dye bath. Therefore, according to the invention, it is advantageous to use water-miscible oxygen Connections used.

The oxygen-containing compound can be used in the same concentration as the metal sulfate, i.e. H. in a concentration of 5.0 to 30.0% by weight, based on the total weight of the dyebath will. It is preferably used in a concentration of 5.0 to 30.0% by weight, based on the total weight of the dyebath. When the concentration of the oxygen-containing compound is less than 3.0% by weight, sufficient effects cannot be obtained by adding it. if on the other hand, its concentration is more than 30.0% by weight, the solubility of the dye becomes excessive good, and the diffusion of the dye into the fibers is prevented. This leads to a reduction in the Dyeability, and even if the fibers can be temporarily dyed, the color has the Tendency to bleed to death. In addition, the swelling effect of the oxygen-containing compound becomes strong and leads to a deterioration in the strength of the fibers.

The metal sulfate and the oxygen-containing compound can be used separately or in combination can be used with each other. If they are both used at the same time, the total amount is of these compounds 3.0 to 35.0% by weight.

The main advantage of this embodiment of the invention is that the amount of the amide compound, which is difficult to remove by washing out of the phenolic fiber motherboard , can be significantly reduced. In this embodiment of the invention, sufficiently improved coloring effects can be obtained even when the amide compound is present in an amount of only 3.0 to 10.0% by weight based on the total weight of the dye bath.

Preferably the concentration of the amide compound is 5.0 to 10.0 wt%. According to this embodiment of the invention in which the metal sulfate or the oxygen-containing compound or bolde are used together with the amide compound, phenolic resin fibers can be used in the same way as when the amide compound is used alone. to be stained. The effect of the metal sulfate or the oxygen-containing compound is not yet clear. However, it is assumed that this is not just a mere swelling effect of a conventional carrier, but that it also increases the solubility of the dye and promotes the diffusion of the dye . In connection with the neutralizing effect on the negative charge on the surfaces of the fibers, which is exerted by the amide compound, these additional compounds can promote the even coloring of phenolic resin fibers in deep, true shades.

The amount of the amide compound can be increased by adding the metal sulfate and / or the oxygen-containing

ίο connection can be reduced significantly. Can also Adsorption of the amide compound on the fibers can be prevented by these added compounds, so that the amide compound can be easily removed by washing. According to the method according to the invention can use the phenolic resin fiber materials, which were previously difficult to dye, evenly in deep shades are colored and the colorations have advantageous fastness properties. Also will the desired incombustibility in this process

ίο the phenolic resin fibers are not affected. The process according to the invention is very advantageous from a technical point of view, since it does not require an additional staining stage. The percentages given in the following examples are based on weight, unless otherwise stated. The dye exhaustion given in the following examples was calculated from the following equation

Dye consumption (%) =

A-A

100

where A is the concentration of the dye in g / l dye bath before dyeing and ß the concentration of the dye in g / l dye bath after dyeing. .15 The colorability (KIS) was calculated according to the following Kubelka-Munk equation:

. | o where R is the reflection of the sample color.

The wash fastness was determined in accordance with JIS-L-1045, die Rubbing fastness according to JIS-L-1048 and the light fastness determined in accordance with JIS-L-1044. The length of the carburization was determined according to the vertical method (JIS-L-1004)

.15 is correct, in which the test fabric (piece of fabric) is vertical and in contact with a flame for 12 seconds using a bunsen burner after which the length of the charred portion of the test fabric was measured. the

Presence of the amide compound remaining in the coloration was determined by the infrared absorption spectrum.

example 1

A smooth woven fabric made from individual yarns of phenolic resin threads that are melt-spun into a Novolak-type phenolic resin and then cured with formaldehyde, were stained with the following dye solution:

Violet disperse dye (C I. No. 61100) N.N'-diethyl acetamide

25% / F-wt.

30% (based on the weight of the dye bath)

Amount of
Dye solution

the 10Of ache of
Weight of the to
coloring material

In this example, as well as in the following examples, the amount of dye was in%, based on the weight of the fiber «(abbreviated»% / F-wt. «).

The fabric was immersed in the dye bath and dyeing was started at 40 C ^0, where the temperature was increased over a period of 30 minutes at 13O ⁰ C, the staining was carried out for 60 minutes. The fabric was then washed in water and then ^{treated for 20 minutes at 80 °} C. with a reducing washing liquid which consisted of 1 g hydrogen sulfite, 1 g anhydrous soda, 1 g of a nonionic surfactant and water per liter, then with water washed and dried. The dyed fabric thus obtained had a deep purple hue. The dye exhaustion was 69.8%.

Subsequently, dyeing was carried out under the same conditions as above using dye baths, which had been prepared in the same way, but this time the content of N, N'-diethylacetamide was varied according to the information in Table 1 below. The received Results are given in Table I below.

Table I.

No amount of amide compound

I.
2
3
4th
5
6th
7th
8th
9
10
11

N.N'-Diälhylacetamide 0%

N.N'-diethylacetamide 3%

N, N'-diethylacetamide 5%

N.N'-dillthylacetamide 10%

N.N'-Dittthylacctamide 15%

N.N'-diethylacetamide 20%

N.N'-diethyl octamide 25%

N.N'-diethylacctamide 30%

N.N'-diethyl octamide 40%

N.N'-diethylacctamide 50%

N.N'-DilUhylncetamide 60%

Dye from
creation (%)

10.0
12.8
40.8
60.8
69.8
67.2
36.5
10.1

3.1

Navy blue Disperse dye

13% / F oew.

From the above results, it can be seen that it is uniform with a deep hue uncolored products were obtained when the content of Ν, Ν'-dlälhylacetamld was above 5%, on the other hand when the amount added was less than 5% or more than 50%, there was a marked decrease in the Dye exhaustion. In addition, the ratings for the light fastness, wash fabric and Relbcchthelt in grades 4,4 and 9.

Example 2

A sliver of the same phenolic resin threads as In Example 1, the following color bath was used stained;

N, N'-dimethylacetamide

Amount of
Dye solution

25% (based on
the weight of the
Dye bath)

20 times the
Weight of the to
coloring material

The top was immersed in the dye bath and dyeing was started at 30 ^° C., then the temperature was ^{increased to 120 °} C. over a period of 30 minutes, dyeing being carried out for 90 minutes and then washing with water. The sliver was then treated for 20 minutes at 8O ⁰ C with a reducing washing liquid per liter of 1 g Hydrogendulfit, 0.5 g of anhydrous sodium carbonate, 1 g of a nonionic surfactant, and water, after which the sliver with water was washed and dried. The resulting colored product had a deep blue tint and the color exhaustion was 90.5%.

The above experiment was repeated for comparison, this time no Ν, Ν'-dimethylacetamide was added or instead of Ν, Ν'-dimethylacetamide phenol, benzyl alcohol or m-dichlorobenzene was added. The results obtained are given in Table II below.

Table II

No. Amide compound content

N.N'-dimethyl acetamide

phenol

Benzyl alcohol

m-dichlorobenzene

Dye- the end creation
(%) 25% 90.5 0% 0 20% 2.0 20% 3.1 20% 0

From the above results, it can be seen that a product uniformly colored with a deep shade was obtained when N.N'-dimethyl octamide was added, but that in the case where the N.N'-dimethyl octamide was not added, no staining was possible. In addition, the dye uptake was 0 or was very low when a carrier, such as. B. phenol, benzyl alcohol or m-dichlorobenzene was added. From these results it is evident that the effect of the amide compound used in the initial phase is not only that of a Currier! is. The ratings of the color fastness to light washing and rubbing were in clusters 4.4 and 5, respectively.

Example 3

One from the phenolic resin threads of the example manufactured knitted fabric was In a Fttrbebud de colored composition given below.

More pinkish Dispersions

dye

30% / F-Oew,

Ν, Ν'-dimethylformamide

Amount of
Dye solution

27% (based on the weight of the dyebath) 60 times the weight of the to coloring knitted fabric

The knitted fabric was immersed in the dye bath and dyeing was started at 40 ° C, then the temperature was raised to 100 ° C. over a period of 30 minutes, at which the dyeing 60 Continued for minutes. The knitted fabric was then washed with water and then 20 Treated for minutes at 80 ° C in a reducing washing bath, which per liter of 1 g hydrogen sulfite, 1 gram of anhydrous soda, 1 gram of a nonionic surfactant, and water; afterward was washed with water and dried. The knitted fabric thus obtained had a red color Color tint on.

The experiment was repeated in the same way as above, but this time no N, N'-dimethylformamide or instead of N, N'-dimethylformamide, formaldehyde was added. The received Results are given in Table HI below.

Table 111

No addition

Dye consumption (%)

N.N'-dimethylformamide

formaldehyde
formaldehyde
formaldehyde

27% 0% 10% 20% 30%

69.8 0 0

2.0 2.5

Blue canonical

dye

(C. I. No. 51004)

Acetanilide

Amount dor
Dye solution

13% / F-wt.

20% (based on the weight of the bath) is equal to the weight of the material to be dyed

After being started with the dyeing at 4O ⁰ C, the temperature was raised over a period of 30 minutes to 125 ° C and then dyeing was continued for 60 minutes at this temperature. The colored material was then washed with water and then ^{treated for 20 minutes at 80 °} C. in a washing liquid which consisted of an aqueous solution of 1 g of a nonionic surface-active agent per liter. The material was then washed with water and dried. The dyed fabric thus obtained had a blue tint.

The experiment was carried out in the same way, but this time instead of acetanilide either Ν, Ν'-diphenylformamide, N, N'-diphenylacetamide, Methylbenzamide, Ν, Ν'-diethylformamide or N.N'-dimethylbenzamide was used. The one with it The results obtained are shown in Table IV below.

Table IV

No addition

From the above results, it can be seen that the mntcrinl has a uniform deep hue could be stained if N.N'-Dimethylformnmid was added but that it could not be colored at all if this was not added became. On the other hand, when formaldehyde was used in place of N.N'-dimethylformumide, the material became in the various concentrations in which the formaldehyde was used, not at all or only weakly stained.

Example 4

One made from the same phenolic resin yarn as in Example I prepared forehand material was put in a bath of the following composition. tongue colored:

Dye exhaustion O)

Acetanilide 20th 87.5 Ν, Ν'-diphenylformamide 20th 86.0 Ν, Ν'-diphenylacetamide 20th 79.6 Methylbenzamide 20th 82.1 N ₁ N 'diethylformamide 20th 72.5 N, N'-dimethylbenzamide 20th 81.5 0 0

.VS As can be seen from the above results, it was possible to create a deep and even tint when acetanilide, N.N'-diphenylformamide, Ν, Ν'-diphenylacetamide, methylbenzamide, N.N'-diethylformamide or N.N'-dimethylbenzamide added

■ was in.

Example 5

A double-layer toilet thread, consisting of the phenolic resin threads of Example 1, was tinted with a dye bath of the following composition:

TI) »lacquer I $ 2S (Dia / o
component of the company
Daito Chemical Co.,
Japan)

TD 1200-2S (coupling component from the company
Dnito Chemical Co.)

Benzane llide Amount of the dye bath

20% (based on the weight of the filrbeiulon material)

30% (based on the weight of the material to be treated)

30% (based on the weight of the building)

the 20fncho of the weight of the material to be colored

After dom start of dyeing at 3O ⁰ C the temperature was raised within a tent space of 20 minutes to 115 ⁹ C, and at this temperature, the dyeing was continued for 90 minutes, then the dyed yarn in water and then washed in hot water. The Oarn was 30mlnüllges plate at 100 ^e C in a Dlazotlerungskupplungsbad consisting of 10% (based on the Gewloht

No addition

of the material to be colored), sulfuric acid and 9% Table VI

(based on the weight of the material to be colored)

Sodium nitrite, after which the yarn was washed with water and dried. The thus obtained dyed product had a deep black tint.

The above procedure was repeated, this time adding benzamide, methylbenzamide, ethylbenzamide, propylbenzamide, N, N'-diethylbenzamide, Ν, Ν'-dipropylbenzamide, instead of benzanilide, the results given in Table V below were obtained.

Dye consumption (%)

1 - 22nd 0 2 Acetoethylamide 20th 75.6 3 Acetopropylamide 20th 68.5 4th Acetoanilide 70.1

Table V

No addition (W

Dye consumption (%)

1 Benzanilide 30th 76.5 2 Benzamide 30th 68.9 3 Methylbenzamide 30th 72.8 4th Ethylbenzamide 30th 69.5 5 Propylbenzamide 30th 43.8 6th N, N'-diethylbenzamide 30th 60.5 7th Ν, Ν'-dipropylbenzamide 52.1 8th 0 0

From the above results it can be seen that the fabric has a deep, even shade of color was colored when acetoethylamide, acetopropylamide or acetanilide was added.

Example 7

A twill fabric made from a 2-ply yarn from the Phenolic resin threads of Example 1 were printed with a printing paste of the composition given below and then subjected to a steam treatment.

It can be seen from the above results that the yarn was dyed in a deep shade was when benzanilide, benzamide, methylbenzamide, ethylbenzamide, propylbenzamide, N.N'-diethylbenzamide or Ν, Ν'-dipropylbenzamide were added.

Black disperse dye Ν, Ν'-dimethylacetamide Sodium alginate water viscosity

Example 6

A fabric (tweed) made of a 2-ply yarn made of the phenolic resin threads of Example 1 was with a Dyebath dyed with the following composition:

Black

Disperse dye Acetoethylamide

Amount of Dye bath that

17% / F-wt.

22% (based on the weight of the Dye bath)

15 times the Weight of the to coloring material

After starting dyeing at 20 ° C, the The temperature inside a tent was raised to 100 ° C from 60 minutes, and then the colored material became washed in water. The dyed fabric was then reductive for 20 minutes at 80 ° C Washed in a reducing wash bath subjected to the per liter of 1 g of hydrogen sulfite, 0.5 g of anhydrous Soda, 1 g of a nonionic surfactant, and water; then it was with water washed and dried. The dyed fabric thus obtained had a deep black hue with a blue stitch on.

The above experiment was repeated, this time using acetopropylamide or instead of acetoethylamide Acetanilide was added. The results obtained are given in Table VI below.

300 g 200 g 50 g 450 g 520OcP

After the execution of printing of the printing paste by the screen printing method, the tissue was immediately treated for 30 minutes at 13O ⁰ C with water vapor and then washed with water. The tissue was then 20 minutes at 8O ⁰ C in an aqueous solution containing 1 g of a nonionic surfactant per liter and subsequently washed with water and dried.

For comparison, the experiment was repeated, but this time without the addition of Ν, Ν'-dimethylacetamide. the The results obtained are shown in Table VII below.

Table VII

45

No addition

Dye consumption (%)

50 2 Ν, Ν'-dimethylacetamide (30) 61.5

From the above results it can be seen that

a printed product was obtained, which in a deep hue when Ν, Ν'-dimeluyl acetamide was added, but not at all was colored when this was not added.

Example 8

A smooth woven fabric made of fibers formed by melt-spinning a novolak-type phenolic resin and subsequent curing with formaldehyde were obtained with a dye solution of the the composition specified below

(-S colors:

CI. Disperse Violet 22

20% / F-wt.

Ν, Ν'-dimethylformamide

Sodium sulfate

Amount of dye bath

added in the amount specified above (based on the weight of the Materials) added in the specified in the following Table VIII Amounts 50 times the weight of the material to be colored

The material to be dyed was immersed in the dye bath and dyeing was started at a temperature of 4O ⁰ C, followed by the

Temperature was raised over a period of 30 minutes at 13O ⁰ C and dyeing was continued for 60 minutes at this temperature. The material was then washed with water and then subjected to a 20 min reductive wash at 8O ⁰ C in a reduction of washing liquid per liter of 1 g of hydrosulfite, 1 g anhydrous sodium carbonate, 1 a g non-ionic surfactant, and water, followed by washed it with water and dried it. The results obtained are shown in Table VIII below.

Table VIII

No addition

Ν, Ν'-dimethyl sodium sulfate formamide

Exhaustion of waste

Char length

(cm) -

Remaining N, N'-dimethylformamide

10

11th

12th

10
10
10
10
10
10

20th
20th

not colored

10

20th

30th

50

30th

30th

30th

10.2 35.6 44.8 52.2 54.9 11.8

16.2
16.2
16.0
16.3
16.2
16.2
16.0
16.0
19.1
20.0
15.8
13.2

From the results of the dye exhaustion measurements given in Table VIII above it can be seen that dye utilization was exceptionally low when the 10% N, N'-dimethylformamide no sodium sulphate was added to the dye solution, but it is increasingly larger when sodium sulfate was added in increasingly larger amounts of 3, 10, 20 and 30%. The addition however, of sodium sulfate in an amount of 50% is not appropriate because of difficulties related to its dissolution occur and also fills the extent of the dye exhaustion. Therefore were themselves in the case of a 10% N, N'-E) imethylformamide solution, the coloring effects are the same as when using a 20% Ν, Ν'-dimethylformamide solution, if 10 to 30% sodium sulfate was added. In addition, the fact shows that there are no dye exhaustion effects occurred when staining using Ν, Ν'-dimethylformamide in an amount of 10% or the sodium sulfate in an amount of 30% were used independently that the synergistic Effects can be attributed to the joint use of these two components.

On the other hand, the fabric dyed according to the present invention exhibited when the charring length, when burned was measured to have a char length in the same order of magnitude as that non-dyed fabrics. This shows that the fabric stained by the method of the present invention was fire resistant. The color fastness values to light, washing and rubbing lagoon in classes 3–4.4 or 5.

Example 9

A two-ply yarn composed of threads melt-spun a novolak-type phenolic resin and subsequent curing with formaldehyde was made with a dye bath colored with the following composition:

CI. Disperse Violet 22

N, N'-diethylformamide

Water soluble
Metal sulfate, as it is in
of the following
Table IX is given.

20% (based on the
Weight of the item to be colored
Materials)

8% (based on the weight of the dye bath)
20% (based on the
Weight of the dye bath)

The material to be dyed was immersed in each of the dye baths containing solutions, the various salts and the material was then stained that was begun with the staining at 40 ⁰ C and

^{then the temperature was increased to 130 °} C. within a period of 30 minutes, the dyeing being continued at this temperature for a further 60 minutes. The colored material was then washed with water and then washed 20

(> 5 minutes, subjected to reductive washing treatment at 80 ⁰ C in a solution containing per liter 1 g of hydrosulfite, 1 g anhydrous sodium carbonate, 1 g of a nonionic surfactant and water

confessed; then it was washed with water and blast dried. The staining and the reductive washing were carried out in liquids, the amount of which was 50 times the weight of the treated material. The results obtained with these stains are given in Table IX below.

Table IX additive Sulfates admitted dye Return No. lot exhaustion permanent Ν, Ν'-diethyl Sodium sulfate 20th N.N'-diethyl formamide
(%) Potassium sulfate 20th <*> formamide 8th Magnesium sulfate 20th 54.7 _ 1 8th Aluminum sulfate 20th 51.7 2 8th Cobalt sulfate 20th 54.7 _ 3 8th Nickelsu'.fat 20th 48.4 4th 8th Potash alum 20th 38.5 5 8th - - 35.8 6th S. - 45.6 _ 7th 8th 8.6 + 8th 20th 40.5 + 9

From the above results it can be seen that practically no dye exhaustion occurred when in of the dye solution only 8% Ν, Ν'-diethylformamide were included, but a marked improvement occurred when 20% of the various salts were used together with 8% Ν, Ν'-dimethylformamide in the dye solution, and that one more higher dye exhaustion rate than in the case of a dye solution containing 20% Ν, Ν'-dimethylformamide occurred when either sodium sulfate, potassium sulfate, magnesium sulfate, or potassium aluminum sulfate Potash was added. About the same rate of dye exhaustion was achieved with cobalt sulfate or nickel sulfate was used. In addition, the concentration (amount used) of N.N'-diethylformamide can be decreased by about half or more. In addition, there was also the disadvantage the flame spread during burning due to the adhesion of the amide compound.

example

A tweed fabric made of a 2-layer yarn, which consisted of the phenolic resin threads of Example II, was immersed in a dyebath of 20% / F-wt. from CI No. Disperse Blue 55 consisted of 10% (based on the weight of the dyebath) of methylbenzamide and 20% (based on the weight of the dyebath) of one of the salts given in Table X below. The dyeing was started at 40 ^° C. and the temperature was increased to 110 ^° C. over a period of 30 minutes, the dyeing being continued at this temperature for a further 90 minutes. The fabric thus dyed became

Table X

then washed in water and then subjected to a 20 min reductive wash at 8O ⁰ C in a solution containing per liter 1 g of hydrosulfite, 1 g of sodium carbonate, 1 g of a nonionic surfactant and water Bestami anhydrous; then "it was washed with water and dried. The staining and reductive washing were carried out in liquids the amount of which was 50 times the weight of the treated material. The results obtained are shown in Table X below."

additive
Methylbenzamide

added salt

Dye-back-carbonization remaining lungs length added amount of methylbenz amide
(%) (%) (cm)

10

10

10

10

10

10

10

not colored

tissue

20th

Sodium sulfate

Sodium acetate

sodium

Sodium phosphate

Lead acetate

Magnesium chloride

3.8 20th 52.5 20th 2.7 20th 3.2 20th 2.9 20th 3.7 20th 4.4 0

50.1

12.1
10.5
10.5
10.6
10.6
10.7
10.8
10.2

12.5

From the above results show that <> s rate equal to that was that when only ^spoil 51J "

a significant improvement in the dye exhaustion of methylbenzamide in an amount of 2OM0

recovery rate occurred when 10% methylbenzamide and 20% was obtained. In the case of using other sai ^

Sodium sulfate have been used together, the as a sulfate, for example by

Sodium acetate,

y / L-

* 11th

Sodium carbonate, sodium phosphate, lead acetate and magnesium chloride, however, the dye exhaustion rate was extremely low and therefore Ρ ™. '* ^η worthless. From this it can be seen that the common use of a salt is only effective at. Use of a sulfate is achieved, the effects of which can be seen from the above results.

Example 11

A curtain material made from individual yarns, consisting of the phenolic resin of Example 8, was immersed in a dyebath consisting of 30% of a pink cationic dye, 8% of Ν, Ν'-dimethylformamide and 25% of sodium sulfate , consisted of 1% of sodium cetyl (penetration agent), and 36% of water, and after padding, the material was wrapped and immediately 60 minutes hei 12O ⁰ C in steam treated, after washing the material in water, it was followed by 20 MmuVen long in a washing liquid (80 ° C.) which consisted of an aqueous solution of 1 g of a nonionic surface-active agent, followed by washing with water and drying.

The above experiment was repeated for comparison. In one case, the experiment was carried out without the addition of NJM'-dimethylformamide carried out, in the other case no sodium sulfate was added and in another case both components were not admitted. The results obtained are given in Table XI below.

Table Xl

additive

Dyeability

Char length

Remaining Ν, Ν'-dimethylformamide

no Ν, Ν'-dimethylformamide and no sodium sulfate were added inventive method 12.91

no Ν, Ν'-dimethylformamide was added 0.35 no sodium sulfate was added 0.59

16.0
16.0
17.5

From the above results it can be seen that the material is deep and uniform Tint was stained when Ν, Ν'-dimethylformamide and sodium sulfate were used together were (inventive method). However, if no Ν, Ν'-dimethylformamide was added or when no sodium sulfate was added, virtually no dye uptake occurred. also was in the combustion test, the char length of the stained according to the method of the invention Product briefly as in the case of staining without adding the other components, which shows that the product colored by the process of the invention was fire resistant.

Example 12

A knitted fabric made of individual yarns made of phenolic resin threads of Example 8 was made by the screen printing process

Table XII

printed with a printing paste, 30% of which consists of a red disperse dye and 10% of acetanilide 10% potassium sulfate, 5% propyl alginate (thickener) and 45% water

\ s and had a viscosity of 6000 cP, thereafter was

'40 minutes treated the knitted fabric immediately at 13O ⁰ C with steam. The knitted fabric was then washed with water and then washed for 20 minutes in a washing liquid which is a

was an aqueous solution containing 1 g of hydrogen sulfite per liter, Containing 0.5 g of anhydrous soda and 1 g of a nonionic surfactant, and then was washed with water and dried. The above experiment was repeated, this time

no acetanilide or potassium sulfate was added. The results obtained are as follows Table XII given.

additive

Dyeability
(K / S)

there were no acetanilide and no potassium sulfate 0.23

admitted

inventive method 11.52

no acetanilide was added 0.37

no potassium sulfate was added 0.48

Char length remaining acetanilide

(cm)

17.2

17.2

17.2

18.2 +

From the above results, it can be seen that when acetanilide and Potassium sulfate a printed product with a beautiful clear green pattern was obtained, but then, when the acetanilide was omitted or when the potassium sulfate was omitted, practically none Color recording took place. In addition, there was no change in char length in any case.

Example 13

A smooth woven fabric made from yarns spun by spinning a novolak-type phenolic resin

23

subsequent hardening with formaldehyde was prepared with a dye solution of the The following composition is colored:

Red disperse dye N, N'-dimethylformamide

Benzyl alcohol

Amount of dye solution

12%

added in the amount given in Table XHl below (based on on the weight of the dye bath)

added in the amount given in the following Table XIH (based on the weight of the dyebath) 50 times the weight of the material to be dyed No. /.iisiii/ and concentration

of the same

creation

N.N'-Di- Bcn / .yl- ■ ^s methyl alcohol

formamide

"■ ■ '* ΙΊΛ. \

Remaining N.N'-dimethylformamide

The material to be dyed was immersed m the dye bath and with the staining beMC began, then was within ej "Z" tnjjs minutes the temperature to ³⁰ J ^ _n! at this

ispssit

given in Table XIH below. Table XIH

No. Addition and concentration of dye of the _{same - test}

Ν, Ν'-di-benzylmethyl alcohol

[SEP * ¹ ww

1
2
3
4th
5
6th
7th
8th
9
10
11
12th
13th
14th
15th
16
17th
18th
19th
20th
21
22nd
23
24
23

0 0 0 0 3 3 3 3 3 5 3 3 5 5 5 10 10 10 10 10 10 10 50 30 30th

3 10 30 50 0 3 10 30 50 0 3 5 10 30 50 0 1 3 5 10 30 30 0 3 5

3.5 35.1 7.2 7.5 0

8.9 36.2 8.1 7.5 11.5 41.5 53.6 56.7 26.8 10.8 15.1 16.2 39.8 89.9 92.3 21.1 12.0 11.5 12.1 13.1 50 50 50 60 60 60 60 60

10

30th

50

10

30th

9.6

7.5

9.1

6.0

4.5

3.2

2.1

From the above results, it can be seen that sufficient dye uptake is not achieved could be obtained when the content of N, N'-dimethylformamide was less than 3%. If on the other hand the content of Ν, Ν'-dimethylformamide exceeded 50%, the dye uptake was also low. aside from that had to be washed more thoroughly because the Ν, Ν'-dimethylformamide remained. When using benzyl alcohol in an amount within of the range of 5 to 30% under such conditions that no Ν, Ν'-dimethylformamide remained , a significant improvement in the rate of color exhaustion achieved, while when the benzyl alcohol in a Amount less than 3% or in an amount greater than 50%, no dye uptake occurred. Example 14

A 2-ply yarn made up of threads that run through Melt spinning of a phenolic resin from Novo-

lak type and subsequent hardening in formaldehyde

ο was obtained with a dye bath the

colored according to the following composition:

Dark brown Dispersion

dye

N.N'-dimethyl

acetamide

Dloxan

Amount of the dye bath

20% (based on the weight of the yarn)

in an amount as indicated in the following table XIV (%, based on the weight of the product) In an amount as indicated in Table XIV below (%, based on dns Weight of the fftrbebado) 20 times the weight of the material to be dyed

(in

The yarn to be dyed was immersed in the bath and dyeing was started at 40 "C, after which the temperature inside a room was increased from 30 minutes to 130" C and dyeing was continued at this temperature for a further few minutes. Thereafter, the Qarn was washed with water, and then it was diluted minutes washed at 8O ⁰ C in a wash liquor containing, per Lltor 1 g of hydrosulfite, 0.3 g of anhydrous sodium carbonate and 1 g of nlcht-lonlsohen surfactant contained, then was treated with Water washed and dried. Those who hold on to it

70ΒΒ31ΛΙΒ7

25th

Results
specified.

Table XIV

are in the following table XIV

No Addition and concentration Dye- Return same (%) the end permanent creation N, N'-Di- N.N'-di-dioxane methvlacet- methyl- amide acetamide (%)

5
10
10
10
10
10
50
50
60
no addition

10 30 0 5 10 30 50 0 5 10 30 50 5 10 5

7.9 15.8 17.1 56.2 77.7 81.6 18.5 23.6 70.1 86.5 28.6 10.0 17.1 15.1 11.2

3.1

As can be seen from the above results, the dye exhaustion rate was low when none N.N'-dimethylacetamide was contained or if this was contained in an amount of more than 50% even with the simultaneous addition of dioxane. In addition, was residual N.N'-dimethylacetamide found. If, on the other hand, you have 5 or 10% Ν, Ν'-dimethylacetamide used together with dioxane were pronounced at a dioxane content of 5 to 30% Dye uptake effects noted. In addition, no residual Ν, Ν'-dimethylacetamide was found.

Example 15

A knitted fabric made of a 2-layer yarn made of threads that are melt-spun from a phenolic resin Novolak type was made with a dye bath of the following composition stained:

More pinkish
ι s disperse dye
The ones in the following
Table XV indicated various
links

Amount of dye bath

18% / F-wt.

in the in the following
Table XV indicated amount (%, based on the weight of the
Dye bath)

20 times the weight of the material to be colored

After the immersion of the above knitted fabric in the s dyebath and after beginning the staining at 4O ⁰ C the temperature was raised over a period of 40 minutes at 13O ⁰ C, and dyeing was continued for a further 60 minutes at this temperature. Then the knitted fabric was made with water

ρ and then in. for 20 minutes at 80 ° C washed a washing liquid, the per liter 1 g of hydrogen sulfite, 0.5 g of anhydrous soda, 0.8 g of a nonionic surfactant and water, after which it was washed with water and

vs dried. The results obtained are in dei Table XV below.

Tabel XV Μ, Η'-Di-
methyl- N, N'-Di-
methyl Add Conc
tration Dye-
the end No. formamide
C *) acetamide
(%) (%) scoop U ng
(%) 8th Benzyl alcohol 6th 89.1 1 8th - n-propnnol 6th 82.1 2 8th _ iso-propanol 6th 71.2 3 8th n-butanol 6th 72.5 4th & _ iso-butanol 6th 70.0 5 8th Dioxane 6th 81.5 6th 8th - Cyclohexane 6th 69.7 7th 8th _ acetone 6th 63.5 8th 8th _ - - 5.0 9 8th Benzyl alcohol 6th 82.6 10 ... 8th n-propanol 6th 80.5 Π 8th Isopropanol 6th 69.1 12th <M 8th n-butanol 6th 67.2 13th _{| -} 8th Isobutanol 6th 59.8 14th IN THE 8th Dioxane 6th 79.1 15th t ~ 8th Cyclohexane β 58.1 16 8th acetone 6th 41.5 17th : 8th mm - 8.0
0 18th
19th

Dimethylformamide containing Fttrbebades - from the above results that "although Fnrbstofiausschttpfungsrate In the case of '' ■ ^ 'show was small, but that was due to the simultaneous use of 6% benzyl alcohol, n-propanol and iso-propam n-butanol, iso-butanol, dioxane, cyclohexane or AceK the absorption rate has been greatly improved.

Example 16

A twill fabric made from threads melt-spun a novolak-type phenolic resin and Subsequent hardening with formaldehyde s were prepared with a dyebath of the colored according to the following composition:

Red cationic dye Ν, Ν'-dimethylformamide

The ones in the following Table XVI indicated various links

Table XVl

18% / F-wt.

10% (based on the weight of the ball) 8% (based on the Weight of dye budc)

No. N.N'-Dimethyl additive

formamide

IO

ι.s

Amount of dye bath

50 times the weight of the one to be dyed Materials

The above fabric was immersed in the dye bath and dyeing was started at 40 ° C, thereafter, the temperature was increased to 110 ° C. over a period of 30 minutes, whereby the Dyeing was continued at this temperature for an additional 80 minutes. The tissue was then immersed in water washed and then washed for 20 minutes at 70 ° C in a washing liquid containing 1 g per liter of a nonionic surfactant, then it was washed with water and dried. The results obtained are given in Table XVI below.

Concentration dye

exhaustion

2
3
4th
5
6th
7th
8th
9

10
10
10
10
10
10
10
10
10

n-propanol

iso-propanol

n-butanol

iso-butanol

Methanol

Methanol

Ethanol

Ethanol

From the above results it can be seen that the dye exhaustion rate was low when using a dye bath containing only 10% Ν, Ν'-dimethylformamide, but that a clear improvement occurred when 10% N.N'-dimethylformamide together with n- Propanol, iso-propanol, n-ßutanol or iso-ßutanol were used. On the other hand, the simultaneous use of methanol or ethanol was worthless in terms of improving the dye exhaustion rate. This shows the effects of the simultaneous use of n-propanol, iso-propanol, n-ßutanol or iso-ßuntanol. ΙΊ

I) c i s ρ i c I 17

A smooth Uowcbo uus Yarns lifted PhcnolharzfUden, dlo by Schmclzvcrsplnnicn a "phenolic resin" from .v> Novolak-type and subsequent hardening with formaldehyde were produced with the colored in the following bath:

Brown dispersion »· 15% / F-wt. Parbitoff

Table XVII

N.N'-Dmelhyl. formamide

ZlUBU

8th 90.8 8th 81.2 8th 83.5 8th 78.6 8th 9.1 30th 8.2 8th 5.2 30th 4.5 - 3.5 N.N'-dimethyl 8% (bc / og ^ n hoof the Gc formamide weight of the filrbchiidcs) The ones in the following 8% (based on mif dus Table XVII Weight of the cylinder) given different links Amount of dye bath the 30fachc of the Ge weight of what is to be colored Materials

The fabric was immersed in the dye bottle and The staining was started at 40 "C, then the temperature was within a space of 40 minutes increased to 128 "C, with the colors 80 Minutes at this temperature. The fabric was then washed in water and then for 20 minutes at 80 "C with a ReduktlonswaschflUsslgkelt treated, dlo per litei 03 g hydrogen sulfite, 0.4 g anhydrous sodate and 1 g a mono-mono surfactant developed held; then it was washed with waiter and unc dried. The results obtained are in doi given in Table XVII below.

Consistency

Ptrbitotf lunch

I. B. n-amyl alcohol 8th 76.5 2 8th Tetranydrofurfuryl alcohol! 8th 69.8 3 B. Methyl ethyl ketone 8th 70.2 4th 8th Ethyl ketone 8th 38.6 K 8th Methyl formate 8th 62.1

29 23 18 762 additive 30th Dye- iuisseluipfunj: continuation N.N'-dimethyl Ethyl formate concentration 68.2 No. formamide
(%) Propyl formate (<> / ") 50.2 8th Methyl acetate 8th 60.5 6th 8th Ethyl acetate 8th 79.3 7th 8th Propyl acetate 8th 58.2 8th 8th Butyl acetate 8th 53.6 9 8th - 8th 7.6 10 8th n-amyl alcohol 8th 12.6 11th 8th Tetrahydrofurfuryl alcohol 0 10.5 12th 0 Methyl ethyl ketone 8th 8.8 13 (control) 0 Diethyl ketone 8th 2.6 14th 0 Methyl formate 8th 5.4 15th 0 Ethyl formate 8th 6.2 16 0 Propyl formate 8th 3.2 17th 0 Methyl acetate 8th 6.5 18th 0 Ethyl acetate 8th 15.1 19th 0 Propyl acetate 8th 7.1 20th 0 Butyl acetate 8th 2.1 21 0 8th 0 22nd 0 8th 23 0 0 24

From the above results it can be seen that the dye exhaustion rate using a dyebath containing only N.N'-dimethylformamide is small, but the dye exhaustion rate can be greatly improved while at the same time

Use of 8% η-amyl alcohol, tetrahydrofurfuryl alcohol, methyl ethyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl .i < > acetate, propyl acetate or butyl acetate.

Claims (1)

Patent claims: 1. A method for dyeing fibers made of phenolic resins, characterized in that that the fibers are treated with an aqueous dye bath containing 3 to 50% by weight as a dyeing aid, based on the total weight of the dyebath, at least one amide compound of the general Formula (I) contains: